Infectious developer composition

ABSTRACT

An infectious developer for photographic plates for printing containing at least one phenol compound represented by the following formula:   WHEREIN R1, R2, R3, R4 and R5 which need not be identical are a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, an alkoxy group, COOM, SO3M where M is a hydrogen atom, a water soluble cation or a hydrocarbon group, a halogen atom, S R6 where R6 is a hydrocarbon group or a substituted hydrocarbon group, COR7 where R7 is a hydrogen atom, a hydrocarbon group or a substituted hydrocarbon group, or NR8R9 where R8 and R9 are a hydrogen atom, a hydrocarbon group or a substituted hydrocarbon group.

United States Patent 1191 Shimamura et al. Feb. 5, 1974 INFECTIOUS DEVELOPER COMPOSITION 3,632,341 1/1972 Zacchia 96/66.4

t h' E" hi k t' Y [75] Inven ors E323 xg ri i- 00 Primary ExaminerNorman G. Torchln Assistant Examiner-M, F. Kelley Mmaml Ashlgara Japan Attorney, Agent, or FirmRichard C. Sughrue et al. [73] Assignee: Fuji llhoto Film Co., Ltd., Ashigara-shi, Kanagawa, Japan I [57] ABSTRACT [22] Filed: Dec. 21, 1971 An infectious developerfor photographic plates for printing containing at least one phenol compound [21] Appl 210546 represented by the following formula:

[30] Foreign Application Priority Data 1 Dec. 21, 1970 Japan 45-115432 [52] US. Cl. 96/66-.4, 96/66 R 51] Int. Cl.-..:.' .[G03c 5/30 [58] Field of Search 96/66, 66.4

[56] R fe nc Cit d wherein R,, R R R, and R which need not be iden- UNITED STATES PATENTS tical are a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, an alkoxy group, 3: 2": COOM, 80 M where M is a hydrogen atom, a water 4673 5/1964 Gauguin" 96/66 soluble cation or a hydrocarbon group, a halogen 3Il861843 6/1965 Haas 96/66 R atom; S R; where R6 is a hydrocarbon group or 3 3,241,964 3/1966 Land 96/66 R substituted hydrocarbon group, COR where R is a 3,257,207 6/1966 Green 96/66 R hydrogen atom, a hydrocarbon. group or a substituted 3,276,873 10/1966 Green 96/66 R hydrocarbon group, or NR R where R and R are a 2 hydrogen atom, a hydrocarbon group or a substituted a e h b 3,576,634 4/1971 Woodward et a1 96/66 R ydrocar on group 8/1971 Haist et a1 96/66 R 9 Claims, N0 Drawings 1 INFECTIOUS DEVELOPER COMPOSITION BACKGROUND OF THE INVENTION 1. Field of the Invention:

The present invention relates to an infectious developer used for making photographic printing plates, particularly an infectious developer having excellent preservability which is used for making photographic plates having good image quality.

2. Description of the Prior Art:

Photographic plate for printing can generally be produced by an infectious development of a lithotype photographic sensitive element typically used for produc ing a dotted or line drawing or a hard photographic sensitive element having'high contrast and forming images of excellent sharpness. Known litho-type sensitive elements include lithofilin or lithoplate which is used for recording images on a printed original having a continuous gradation density by dividing the images into meshed dots so that a variation in density changes into a variation in the area of the dots,and litholine film or litholine plate which is used for a printed original having line drawings. I

In order to divide the image into the meshed dots, a cross line glass screen or a contact screen is used, A half-tone plate is obtained by printing the image of the original onto the litho-type sensitive element through a screen and conducting development.

An ideal half-tone plate consists of dotted spots having a maximum density and a background having a minimum density. .However, since any-hard photographic sensitiveelement has an intermediate density, areas of intermediate density, called fringe areas, are always formed around the dots. Fringe is not desirable for plate making because it notably deteriorates the quality of printed images. The line drawing image is thought of as continuous series of dotted images. Accordingly, in litholine film or plate, areas of intermediate density are not desirable.

The developer used for producing photographic plates for printing using a lithotype sensitive element or another hard sensitive element is usually an alkaline infectious developer which contains a dihydroxybenzene type developing agent and an aldehyde-alkali hydro gen sulfite addition product as the preservative. Infectious developers of this kind have poor preservability as compared to common black-white developers because the amount of a free sulfite ion is small.'In a developer having a low free sulfite ion concentration, the life of activated hydroquinone is kept for a long period of time and the hydroquinone is infectively activated and accumulated thereby. Consequently, images having a high contrast and low fringe are obtained since the development is carried out rapidly.

However, in developers having a high free sulfite ion concentration, the life of the activated hydroquinone is short and the hydroquinone is not accumulated. Consequently, images having a low contrast and high fringe are obtained since the development is not carried out rapidly. There is thus an interaction between the free sulfite ion concentration and the quality of the images obtained on the photographic plate for printing.

Since it is essential for an infectious developer to have a good preservability, it is necessary to improve the preservability by adding an antioxidant other than the sulfite. For instance, it is known to add ascorbic acid to an infectious developer (.lap. Pat. Pub. Sho 44-28673). However, ascorbic acid has a poor stability because it is easily decomposed and it is particularly unstable when metal-ions, such as copper or iron ions exist in the developer. Consequently the preservability of the developer is poor. Moreover, ascorbic acid has the fault that it somewhat hinders the progress of the development and causes deterioration of the quality of half-tone dots if added in large amounts.

The present inventors have found a fact that the preservability of an infectious developer is remarkably improved without bad influence upon image quality by adding atleast onephenol compound represented by the following formula to the infectious developer:

wherein R R R R and R can be identical or-different and can represent a hydrogen atom, hydrocarbon group, substituted hydrocarbon group, alkoxy group, COOM, $0 M (M represents a hydrogen atom,'a water soluble cation or a hydrocarbon group), halogen atom, S R (R represents a hydrocarbon group or substituted hydrocarbon group), COR, (R represents a hydrogen atom, hydrocarbon group or substituted hydrocarbon group) or NR R (R and R represent each a hydrogen atom, hydrocarbon group or substituted hydrocarbon group.

The object of the present invention is to provide a developer especially for photographic plate for printing, which does not have a bad influence upon the quality of the formed images and has excellent preservability.

DETAILED DESCRIPTION OF THE INVENTION:

In the following, typical examples of the compounds used in the presentinvention are shown. However, the scope of the present invention is not limited to these compounds.

Compound number R1 R2 R3 R4 R5 H. H H. H. H. II. CH3. II. ClIa. lI. Ulla. l2 CH II CH3 II (illn- II (JIM. ()Ih Clin- N(CHa)z H.

HO 43411, CH H H.

118, t-C4Hn t-C4Hn t-C4Hn H H.

CH2 0H Pat. NO. 3790383 119 ISO-C3117 ISO-C3117 iSO-Cl H7 H H.

CH -OH iso-CaHv 120 t-C4H9 CH3 t-C4Hn H -CH2 -OH 121 t-Cl D H(|) t- C Hn CzHa H H I CzHs 122 t-C4H0 HO t-C4H9 t-C4H9 H H CH H H.

CHa-.. H...---..-...--.....--. H.

1 6 H H OH; H H- 127 is0-CaH1 .Iffif. 10411. H 1! -on JJH:

128 30 H CH; 11 n.

129 HO H c1 H n Compound number R R: R: Rt Rs io :j:::.TcIfiL H .1.1: t-clm H cm.

'EH OH 131 t-C4Hq HO t-CaHa CHs. H H,

132 t-CrHn H t- 4Ho H CH3.

S OH

133 ..-t-C4Hq H v0.11. cm H H.

These compounds which are all knoVn are dies (5E5? The Inhibition of Fat Oxidation Processes written by N.M. Emanuel and Y.N. Lyaskovskaya (Pergamon Press Ltd., 1967) and Atmospheric Oxidation and Antioxidation written by G. Scott (Elsevier Publ. Co., 1965). They are commonly available.

Practical uses for the compounds used in the present invention were heretofore unknown. Especially, it has not been known at all to improve the preservability of a developer by adding the compounds to any developer, not to mention a developer for photographic plate for printing.

As the result of examinations regarding many kinds of compounds, the present inventors have found that the preservability of the developer is improved by using compounds of the above-described general formula. The reason why the preservability is improved by addition of these compounds to the developer of the photographic plate for printing is unknown.

The preservability of the developer, however, is greatl improved as compared to the use of known preservatives such a; sodium sulfite ascorbic acidTetEf and the resulting photographic images have excellent; quality with low fringe and excellent dots. Moreover,

delay in the progress of the development which is observed with prior art developers is not observed when using the compounds of the present invention.

Though any compound of the present invention represented by the above-mentioned formula is effee- I tive for improvingthe preservability of infectious developers, those which are substituted by at least one alkyl group are preferred and those havingan alkyl group with many carbon atoms are most preferred and specific carbon ranges of more preferred groups are more than 2. in this case, the solubility of the compound is important. For the purpose, water-soluble groups such as sulfon, carboxyl or hydroxyalkyl groups may be bonded to the nuclei with the substituted hydrocarbon. The most preferred carbon ranges are 3 to 5. i

Further, compounds in which the ortho positions of the'benzene ring is substituted by one or preferably two alkyl groups are especially effective. Among these compounds, sterically hindered phenols such as those having an isopropyl group, a t-butyl group or a t-amyl fectiveto introduce a sulfo group, a carboxyl group 6% a hydroxyalkyl group 'in addition to the alkyl groups in order to increase the water-solubility of these compounds.

The water-soluble cations are an alkali metal such as sodium or potassium, and ammonium group.

The developer-for photographic plates for printing to which the compounds of the present invention are added is the common infectious developer which contains hydroquinone as the developing agent. The developer may also contain water-soluble acids, alkalies and salts such as sodium carbonate, sodium hydroxide, acetic acid and boric acid as an alkali agent or a pH buffer agent, aldehyde-alkali hydrogen sulfite addition products, ketone-alkali hydrogen sulfite addition products, sulfites or two or more thereof as an antioxidant, and "alkali halides as a development controlling agent in addition to the hydroquinone. The developer may contain, if desired, organic antifogging agents such 'as benzotriazole and 1-phenyl-5-mercapto-tetrazole, polyalkylene oxides, amine compounds or organic solvents such as triethylene glycol, dimethylformamide, methyl alcohol and cellosolve in the amount of l 300 ml per liter of the developer.

The primary characteristicof prior art infectious de- 1 as shown above. Therefore, a sulfite ion buffer such as a formaldehyde-sodium hydrogen sulfite addition prodact is used. In general, the free sulfite ion concentration is controlled by additionally adding sulfite such as alsuch as formaldehyde-sodium hydrogen sulfite addition product, or a ketone-alkali hydrogen sulfite such as acetone-sodium hydrogen sulfite addition product.

Other examples ofaddition products are described U.S. Pat. No. 3,573,914. Usuallyup to about 3 g of sulfite is added by which the preservability of the developer is somewhat improved, though the quality of halfgroup are especially preferred. It is also especially ef-f A tone dots somewhat deteriorates. However, as shown above, such a degree of preservability is not satisfactory. According to the present invention, the preservability is remarkably improved by adding the abovementioned compounds to the infectious developer containing no alkali sulfite other than a sulfite ion buffer such as formaldehyde-sodium sulfite addition product, and the preservability can be remarkably improved by adding to the infectious developer less than g (per liter of the developer) of an alkalisulfite in addition to the sulfite ion buffer. Sulfite may be added to the developer with the compound of the invention, whereby the developer shows stronger preservability than that containing only sulfite.

TSEQitil com Ti entsb f the inretiaus aeveiabaiai' hydroquinone, an addition product and the compound of the invention.

to 30 g, per one liter of developer.

A range of additional product is to 100 g, preferably to 70 g, per one liter of developer.

"in the above essential components, alkali should be added; but the amount thereof may be such amount that pH of the developer is alkali property, especially pH 8 or more, and more preferably pH 9 pH 11.

case that the developer is prepared as a liquid or powder composition and mixed, diluted or dissolved at the time of use, it is effective at that time to previously add the compounds of the present invention to the composition. in the case of using a liquid composition, it is particularly effective to add the compounds to such a liquid composition because the preservability of the liquid compositionis remarkably increased by the addition of the compounds. Common liquid compositions consist of two liquids, that is, one part containing the developing agent, a second part containing an alkali. Although the compound of the present invention may be added to either part, it is more preferred to add to the part containing the developing agent, by which the preservability of the liquid developer can be further improved and the stability of the developer after preparation of the infectious developer by dilution can be remarkably improved. As another method; it is possible to improve the preservability of the developer by adding the compounds of the present invention during or after development of the photographic plate for print- As emulsions used to form photographic plates for printing, common silver halide photographic emulsions.

chlorobromide, silver bromoiodide and silver chloro- 60 veloper are shown in Table 1.

' A range of h araqu'man is 5 to 56g; preferably 16 present invention vare added at the preparation of the developer. In the bromoiodide can be used. Particularly, silver chlorobromide is suitably used. These silver halides are dispersed in gelatin or a medium comprising gelatin and a synthetic high molecular substance to form an emulsion. The emulsion may be chemically sensitized by compounds containing unstable sulfur such as sodium such as formaldehyde or mucochloric acid, and may contain surface active agents such as saponin so as to make application easy. These additives are added for their well known prior art functions in conventional amounts.

The following examples of the present invention are presented to illustrate the excellent effects of the present invention.

EXAMPLE 1 sensitized with gold and sulfur and then spectrally sensitized with 3-carboxymethyl-5-[ 2-( 3- ethylthiazolinidene)-ethylidene] rhodamine, said emulsion containing polyoxyethylene nonylphenyl ether having ethylene oxide group number of 50, mucochloric acid and polybutylmethacrylate.

Developer A Sodium carbonate (monohydrate) 50 g Formaldehyde-sodium hydrogen sulfite addition 45 g product Potassium bromide 2 g Hydroquinone 18 g Sodium sulfite 2 g Water to make 1 liter Developer B Same as Developer A with 0.05 g of Compound 61 of the present invention added.

Developer C Same as Developer A with added.

Developer D 2- gof sodium sulfite Same as Developer A with l g of L-ascorbic acid added.

The photographic properties obtained using each de- TABCE' 1' I Sensitivity Developer Additives Amount (g/l) Time of Quality of Fresh liquid Elapsed liquid development half-tone dot (minute) A 2% a 100 34 8 Compound 6l 0.05 2% a 100 Q- Sedium sulfite. a... AMW 'L EH. 52 D L-Ascorbic acid L0 3 a 100 50 1 1 i The time of development was that necessary to reach the sensitivity obtained by developing for 2 minutes with Developer A (this sensitivity is regarded as 100).

The quality of the half-tone dots is denoted by 3 ranks a, b and c, that is, a means excellent, b means fairly good and c means worse. The term elapsed liquid means the developer has been subjected to deterioration by contacting 500 ml of the developer in a 20 cm X 25 cm development vat with the air for 5 hours.

As is clear from Table 1, the-sensitivity of Developer A (control) deteriorates largely with lapse of time. The sensitivity of. comparison prior art Developer C in which 20 g of sodium sulfite is added lowers considerably with lapse of time, though deterioration is less than that of Developer A. Further, the efficiency of halftone dot formation in the fresh liquid is worse than for Developer A. Deterioration of the sensitivity of Developer D in which 1.0 g of L-ascorbic acid is added is nearly equal to that of Developer C, not yet satisfactory.

In Developer B, containing 0.05 g of Compound 61 of the present invention, deterioration of sensitivity with lapse of time is the lowest and the deterioration of the quality of the half-tone dots in the fresh liquid is not At use, Solution I was added to 750 ml of water and Solution II was added thereto to provide 1 liter of the final solution to be used.

5 W brsvELoPEii ljeteri oratfii iii theseiisitivityof "niaeviabei containing Compound 29 is less than that of the developer not containing the compound. 15

"Emits"? After hoegta hiayaaitgs uiwage 51855 tometry through a ISO-line contact screen using an available lithofilm, the film was developedat 20 C with developers having the following compositions. I

observed to any significant extent. 5

EXAMPLE 2 Developer G After photographing an exposure wedge for sensitometry through a ISO-line magenta contact screen using an available lithofilm, the film was developed at Sodiumvarbonate'(monohydraw) 40 2 20 C using developers prepared from two kinds of ggzf g hydmge sun-"e 60 g components having the following compositions. Potassium bromide 2 g Boric acid 3 3 Developer E Hydfoquimme 18 s Sodium sulfite 2 g Water to make I liter Solution 1 Distilled water 60 ml Triethylene glycol 30 ml Formaldehyde-sodium hydrogen sulfite addition 45 3 product Hydroquinone I63 H Distilled water to make 125 ml Solution ll D V Distilled water 100 ml E ELOPERS K M N Sodium carbonate (monohydrate) 30 g Sodium h droxide 5 "-2 Bork g 3 5 Those were prepared by adding Compounds 71 74, Sodium bromide 2 g 8 8 9 Distilled water wmake 125 ml 2, 6 3, 96 and 98, respectively, to Developer G.

The results of development are shown in Table 3.

TABLE 2 I i A Sensitivity Developer Additive 'Amount (g/I) Time of Quality of Fresh liquid Elapsed liquid development half-tone dot 7 (minute) 2% a 100 31 F Compound 29 0.2 2% a I00 i i i m "TABLEG Sensitivity Developer Additive Amount (g/I) Time of Quality of Fresh liquid Elapsed liquid development half'tone dot (minute) G 2% a 100 35 H Compound 7| 0.02 2% a I00 l Compound 74 I.I0 2% a 90 1 Compound 82 1.20 2% a 100 75 K Compound 86 2.00 2% a I00 74 L Compound 93 2.00 2% 11 I00 73 M Compound 96 2.00 2% a I00 80 N Compound I08 L50 2% 0 I00 In the developers containing the compounds of the present invention the quality of the half-tone dots did not lower and deteriorate in sensitivity with lapse of time being low, meaning excellent preservability.

EXAMPLE 4 After photographing an exposure wedge for sensitometry through a lSO-line contact screen with an available lithofilm, the film was developed at 20 C with Developer developers having the following compositions.

Developer 0 Solution l Distilled water 7 50 ml Dimethylformamide 30 ml Formaldehyde-sodium hydrogen sulfite addition 45 g product Potassium sulfite g Hydroquinone '16 g Distilled water to make 125 ml Solution ll Distilled water 100 ml Potassium carbonate 1 40g Potassium hydroxide 4 g Glacial acetic acid 2 ml Potassium bromide 2 g Distilled water to make 125 ml DEVELOPERS P, Q, R, S AND T These were prepared by adding Compounds 117, 121, 131, 132 and 133, respectively, in an amount of 0.03 g/l to Solution l of Developer 0 prior to combination with water and solution. The results of development are shown in Table 4.

amount of hydroquinone does not lower as much, and the developer endures for long periods of preservation.

EXAMPLE 6 25 l. of Developer E in Example 2 was supplied to two automatic developing devices for plate making. 200 sheets of half-cut lithofilm were treated while adding a supplementary solution having the following composition in an amount of 70 ml per sheet of half-cut lithofilm.

Supplementary hfia Solution l Distilled water ml Triethylenegylcol 45 ml Formaldehyde sodium hydrogen sulfite addition 45 g product Hydroquinone 20 g Distilled water to make l25 ml Solution ll Distilled water lOO ml Sodium carbonate 30 g Sodium hydroxide 5 g Boric acid I g Distilled water to make 125 ml it use, Solution 1 was added 6 750 niiofiiieihd Solution ll was then added thereto to provide 1 liter of the solution to be used.

After developing the lithofilm, one of the automatic developing devices was left as it stands, and 75 ml of a 1 percent methanol solution of Compound 62 of the present invention was added to the other automatic developing apparatus. After leaving both automatic developing devices for 64 hours, the lithofilms were then TABLE 4 Sensitivity Developer Additive Amount (g/l) Time of Quality of Fresh liquid Elapsed liquid development half-tone dot (minute) 0 2% a 100' 34 P Compound ll7 0.03 2% a 100 73 Q Compound l2l 0.0 3 w 7 2% a 100 74 R Compound l3l 0.03 2% a l00 85 S Compound l32 0.03 I 2% a I00 97 T Compound 133 0.03 2% a 100 92 In the developers containing the compounds of the present invention the quality of the half-tone dots was not lowered and deterioration in the sensitivity with lapse oitime was low, meaning excellent preservability.

ExAMPLE 5 TABLE 5 Remaining amount of hydroquinone Developer E 90 Developer F 99 r8150? frorrT l able 5 55k in concentrated Solution 1 containing Compound 29 of the present invention, the

deemed. maraaaeiapa assaraanawnrch'ma compound of the present invention was added, deterioration of the sensitivity was not observed at all, but in the developing apparatus to which the compound of the present invention was not added, notable deterioration of the sensitivity was observed. Same results as in the former examples could be obtained.

While the invention has been particularly shown and described with reference to preferred emobdiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.

What is claimed is:

1. An infectious developer for photographic plates for use in printing which comprises:

1. hydroquinone as the sole developing agent,

2. a free sulfite in a concentration of less than 5 grams per liter, and 3. at least one phenol compound represented by the following formulaz wherein R R R R and R which need not be identical, represent a member selected from the group consisting of a hydrogen atom, a lower alkyl group, a lower alkoxy group, a COOM group, an M group wherein M represents a member selected from the group consisting of a hydrogen atom, a water-soluble cation, a lower alkyl group, a halogen atom, an S-R group wherein R is identical to the phenol residue to which the S atom is affixed and a COR, group wherein R represents a member selected from the group consisting of a hydrogen atom and a lower alkyl group.

2. The developer of claim 1 wherein said developer further contains a member selected from the group consisting of an aldehyde-alkali hydrogen sulfite addition product and a ketone-alkali hydrogen sulfite addition product.

3. The developer of claim 1 wherein said developer has a pH offrom 9 to 11.

4. The developer of claim 1 wherein said phenol compound has at least one alkyl group having more than 2 carbon atoms.

5. The developer of claim 4 wherein said alkyl group has a carbon range of from 3 to carbon atoms.

6. The developer of claim 5 wherein said alkyl group is a member selected from the group consisting of an isopropyl group, a t-butyl group and a t-amyl group.

7. The developer of claim 1 wherein said phenol compound has a water-soluble group attached thereto,

selected from the group consisting of a sulfone group, a carboxy group and a hydroxyalkyl group.

8. The developer of claim 1 wherein at least one of R and R in said phenol compound is a lower alkyl group.

9. A method for developing a photographic printing plate which comprises:

1. exposing said plate so as to obtain a latent image and 2. developing said exposed plate with an infectious developer comprising: I a. hydroquinone as the sole developing agent, b. a free sulfitein a concentration of less than 5 grams per liter, and c. at least one phenol compound represented by t f w. ns formula:

wherein R,, R R R and R which need not be identi-v v cal, represent a member selected from the group consisting of a hydrogen atom, a lower alkyl group, a lower the S atom is affixed and a COR group wherein R represents a member selected from the group consist- 19119 hxqr r ma.ale aalls lsteva- 

2. developing said exposed plate with an infectious developer comprising: a. hydroquinone as the sole developing agent, b. a free sulfite in a concentration of less than 5 grams per liter, and c. at least one phenol compound represented by the following formula:
 2. The developer of claim 1 wherein said developer further contains a member selected from the group consisting of an aldehyde-alkali hydrogen sulfite addition product and a ketone-alkali hydrogen sulfite addition product.
 2. a free sulfite in a concentration of less than 5 grams per liter, and
 3. The developer of claim 1 wherein said developer has a pH of from 9 to
 11. 3. at least one phenol compound represented by the following formula:
 4. The developer of claim 1 wherein said phenol compound has at least one alkyl group having more than 2 carbon atoms.
 5. The developer of claim 4 wherein said alkyl group has a carbon range of from 3 to 5 carbon atoms.
 6. The developer of claim 5 wherein said alkyl group is a member selected from the group consisting of an isopropyl group, a t-butyl group and a t-amyl group.
 7. The developer of claim 1 wherein said phenol compound has a water-soluble group attached thereto, selected from the group consisting of a sulfone group, a carboxy group and a hydroxyalkyl group.
 8. The developer of claim 1 wherein at least one of R1 and R2 in said phenol compound is a lower alkyl group.
 9. A method for developing a photographic printing plate which comprises: 